Novel microbiocides

ABSTRACT

Compounds of the formula (I) in which the substituents are as defined in claim  1  are suitable for use as microbiocides.

The present invention relates to novel microbiocidally active, inparticular fungicidally active, thienyl/benzthienyl ethyl amides. Itfurther relates to intermediates used in the preparation of thesecompounds, to compositions which comprise these compounds and to theiruse in agriculture or horticulture for controlling or preventinginfestation of plants by phytopathogenic microorganisms, preferablyfungi.

Thienyl ethyl amides and their use as fungicides are described in WO2006/108791 and EP 1710237 A1. Benzthienyl ethyl amides and their use asfungicides are described in WO 2007/006739.

It has been found that novel thienyl/benzthienyl ethyl amides havemicrobiocidal activity. The present invention thus provides compounds ofthe formula I

whereinR₁, R₂ and R₄ independently of each other are hydrogen, halogen, C₁-C₄alkyl or C₁-C₄ halogenalkyl;X is oxygen, sulfur, —N(R₉)— or —N(R₁₀)—O—;R₉ and R₁₀ independently of each other are hydrogen or C₁-C₆alkyl;R₃ is C₁-C₆alkyl or C₁-C₆haloalkyl;

Q is Q₁

or Q is Q₂

whereineach R₅ independently of each other is halogen, C₁-C₄ alkyl, C₁-C₄halogenalkyl, phenyl, halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenylacetynyl or halogenphenyl acetynyl;n is 1, 2 or 3;m is 1, 2, 3 or 4;A is a 5- or 6-membered heterocyclic ring containing one to threeheteroatoms, each independently selected from oxygen, nitrogen andsulphur, or a phenyl ring; the heterocyclic ring or the phenyl beingsubstituted by the groups R₆, R₇ and R₈;R₆, R₇ and R₈ are each, independently, hydrogen, halogen, cyano, nitro,C₁₋₄ alkyl, C₁₋₄ halogenalkyl, C₁₋₄ halogenalkoxy, C₁₋₄alkoxy(C₁₋₄)alkyl or C₁₋₄ halogenalkoxy(C₁₋₄)alkyl, provided that atleast one of R₆, R₇ and R₈ is not hydrogen;R₁₅ is hydrogen or C₃-C₇cycloalkyl; and tautomers/isomers/enantiomers ofthese compounds.

According to the invention, the term “acetynyl”, as used in thedefinition of substituent R₅, is the group “—C≡C—”. As example, C₃cycloalkyl acetynyl is the group

and is present, for example, as substituent R_(5b) in compound 1.17.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, n-butyl, sec-butyl,iso-butyl or tert-butyl. Alkoxy, alkenyl and alkynyl radicals arederived from the alkyl radicals mentioned. The alkenyl and alkynylgroups can be mono- or di-unsaturated.

The cycloalkyl groups occurring in the definitions of the substituentsare, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl orcycloheptyl.

Halogen is generally fluorine, chlorine, bromine or iodine, preferablyfluorine, bromine or chlorine. This also applies, correspondingly, tohalogen in combination with other meanings, such as halogenalkyl orhalogenalkoxy.

Halogenalkyl groups preferably have a chain length of from 1 to 4 carbonatoms. Halogenalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy,isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.Halogenalkoxy is, for example, fluoromethoxy, difluoromethoxy,trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy andtrifluoromethoxy.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl orisopropoxyethyl.

Halogenphenyl is preferably phenyl substituted by 1, 2 or 3 halogenatoms, for example 4-chloro-phenyl.

In the context of the present invention a “5- or 6-membered heterocyclicring containing one to three heteroatoms, each independently selectedfrom oxygen, nitrogen and sulphur” preferably means pyrazolyl(especially pyrazol-4-yl), thiazolyl (especially thiazol-5-yl), pyrrolyl(especially pyrrol-3-yl), 1,2,3 triazolyl, oxazolyl (especiallyoxazol-5-yl), pyridyl (especially pyrid-3-yl) or 2,3dihydro-[1,4]oxathiinyl (especially 2,3 dihydro-[1,4]oxathiin-5-yl).

The compounds of formula I can occur in different isomeric forms; theinvention covers all those isomers and mixtures thereof. The compoundsof the formula I may occur in different tautomeric forms. For example,compounds of formula I exist in the tautomeric forms I_(I) and I_(II):

The invention covers all those tautomeric forms and mixtures thereof.

Preferred are compounds of formula I, wherein R₁₅ is hydrogen.

In a preferred group of compounds A is a 5-membered heterocyclic ringcontaining one to three heteroatoms, each independently selected fromoxygen, nitrogen and sulphur; the heterocyclic ring being substituted bythe groups R₆, R₇ and R₈.

Within said preferred group of compounds, further preferably A is A₁

in whichR₁₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl;R₁₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl; andR₁₈ is hydrogen, halogen or cyano;

or A is A₂

in whichR₂₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; andR₂₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl;

or A is A₃

in whichR₃₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl;R₃₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl; andR₃₈ is hydrogen, halogen or cyano;

or A is A₄

in whichR₄₆ and R₄₇ independently of one another are halogen, cyano, nitro,C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl.

Within said preferred group of compounds, further preferably A is A₁.

Within said preferred group of compounds, further preferably A is A₂.

Within said preferred group of compounds, further preferably A is A₃.

Within said preferred group of compounds, further preferably A is A₄.

In another preferred group of compounds A is a phenyl ring or a6-membered heterocyclic ring containing one to three heteroatoms, eachindependently selected from oxygen, nitrogen and sulphur; the phenylring or the heterocyclic ring being substituted by the groups R₆, R₇ andR₈.

Within said preferred group of compounds, further preferably A is A₅

in whichR₅₆ is halogen, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy orC₁-C₄halogenalkoxy-C₁-C₄alkyl;

or A is A₆

in whichR₆₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl;

or A is A₇

in whichR₇₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl.

Within said preferred group of compounds, further preferably A is A₅.

Within said preferred group of compounds, further preferably A is A₆.

Within said preferred group of compounds, further preferably A is A₇.

In a particular preferred group of compounds A is A₁, wherein R₁₈ ishydrogen. In another particular preferred group of compounds A is A₁,wherein R₁₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl, preferablyC₁-C₄halogenalkyl; R₁₇ is C₁-C₄alkyl; and R₁₈ is hydrogen or halogen,preferably hydrogen.

In another particular preferred group of compounds A is A₂, wherein R₂₆is C₁-C₄alkyl or C₁-C₄halogenalkyl; and R₂₇ is C₁-C₄alkyl.

In yet another particular preferred group of compounds A is A₃, whereinR₃₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl; R₃₇ is C₁-C₄alkyl; and R₃₈ ishydrogen or halogen.

In yet another particular preferred group of compounds A is A₄, whereinR₄₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl; and R₄₇ is C₁-C₄alkyl.

In yet another particular preferred group of compounds A is A₄, whereinR₄₆ halogenmethyl, preferably R₄₆ is selected from CF₃, CF₂H and CFH₂;and R₄₇ is C₁-C₄alkyl.

In yet another particular preferred group of compounds A is A₅, whereinR₅₆ is halogen or C₁-C₄halogenalkyl.

In yet another particular preferred group of compounds A is A₆, whereinR₆₆ is halogen or C₁-C₄halogenalkyl.

In yet another particular preferred group of compounds A is A₇, whereinR₇₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl.

In a preferred group of compounds R₁, R₂ and R₄ independently of eachother is hydrogen or methyl. In one embodiment, R₂ and R₄ are bothhydrogen and R₁ is methyl. In one embodiment, R₁, R₂ and R₄ are allhydrogen.

In a preferred group of compounds X is oxygen or sulfur.

In a preferred group of compounds X is oxygen.

In a further preferred group of compounds X is sulfur.

In yet a further preferred group of compounds X is —N(R₉)—.

In yet a further preferred group of compounds X is —N(R₁₀)—O—.

In a preferred group of compounds R₃ is C₁-C₆alkyl, preferably methyl orethyl. In one embodiment, R₃ is methyl. In another embodiment, R₃ isethyl.

In one embodiment Q is Q₁ (thienyl ethyl amides).

In one embodiment Q₁ is Q_(1A)

wherein R₅ and n are as defined under formula I (thien-2-yl ethylamides).

Preferably, Q_(1A) is Q_(1A-1)

wherein R_(5a) is halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl; R_(5b) is halogen, C₁-C₄ alkyl, C₁-C₄halogenalkyl, phenyl, halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenylacetynyl or halogenphenyl acetynyl; and R_(5c) is hydrogen, halogen,C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl, halogenphenyl, C₃-C₇ cycloalkylacetynyl, phenyl acetynyl or halogenphenyl acetynyl.

In yet more preferred compounds within this embodiment, R_(5a) ishalogen, more preferably chloro; R_(5b) is halogen, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl; and R_(5c) is hydrogen. These compounds areshown in tables 1 to 13.

In one embodiment Q₁ is Q_(1B)

wherein R₅ and n are as defined under formula I (thien-3-yl ethylamides).

Preferably, Q_(1B) is Q_(1B-1)

wherein R_(5a) is halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl; R_(5b) is halogen, C₁-C₄ alkyl, C₁-C₄halogenalkyl, phenyl, halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenylacetynyl or halogenphenyl acetynyl; and R_(5c) is halogen, C₁-C₄ alkyl,C₁-C₄ halogenalkyl, phenyl, halogenphenyl, C₃-C₇ cycloalkyl acetynyl,phenyl acetynyl or halogenphenyl acetynyl.

In more preferred compounds within this embodiment, R_(5a) and R_(5b)are both independently from each other halogen, more preferably chloro;and R_(5c) is halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl. These compounds are shown in tables 14 to 20.

In further more preferred compounds within this embodiment, R_(5a) andR_(5c) are both independently from each other halogen, more preferablychloro; and R_(5b) is halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl. Also these compounds are shown in tables 14 to20.

In one embodiment Q is Q₂ (benzthienyl ethyl amides).

In one embodiment Q₂ is Q_(2A)

wherein R₅ and m are as defined under formula I (benzthien-2-yl ethylamides).

Preferably, Q_(2A) is Q_(2A-1)

wherein R_(5a) and R_(5b) are each independently from each otherhalogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl, halogenphenyl, C₃-C₇cycloalkyl acetynyl, phenyl acetynyl or halogenphenyl acetynyl; andR_(5c) is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl.

In yet more preferred compounds within this embodiment, R_(5a) ishalogen, more preferably chloro; R_(5b) is halogen, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl; and R_(5c) is hydrogen. In one embodiment,R_(5b) is in the 5′-position of the benzthiophene. In anotherembodiment, R_(5b) is in the 6′-position of the benzthiophene. Theseembodiments is represented by compounds of tables 21 to 33.

In one embodiment, Q₂ is Q_(2B)

wherein R₅ and m are as defined under formula I (benzthien-3-yl ethylamides).

Preferably, Q_(2B) is Q_(2B-1)

wherein R_(5a) and R_(5b) are each independently from each otherhalogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl, halogenphenyl, C₃-C₇cycloalkyl acetynyl, phenyl acetynyl or halogenphenyl acetynyl; andR_(5c) is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl.

In yet more preferred compounds within this embodiment, R_(5a) ishalogen, more preferably chloro; R_(5b) is halogen, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl; and R_(5c) is hydrogen.

The preparation of compounds of formula I, wherein R₁₅ is hydrogen, isshown below. Compounds of formula I, wherein Q is Q_(1A-1); R₂ and R₄are both hydrogen; R_(5a) and R_(5b) are both independently from eachother chloro or bromo; and R_(5c) is hydrogen (compounds of formula IAaccording to scheme 1) may be prepared according to scheme 1.

A thiophene-2-aldehyde of formula VA can be reacted with a nitroalkaneof the formula R₁CH₂NO₂, wherein R₁ is as defined under formula I toform the nitroalkenes of formula IVA, in which R₁ is as defined underformula I. Said reaction is carried out conveniently in the presence ofacetic acid and ammonium acetate at temperatures between ambienttemperature and reflux temperature.

The nitroalkene of formula IVA can be reacted with a compound of theformula MXR₃, wherein M is Li, Na or K; X and R₃ is as defined underformula I, to form the nitroalkanes of formula IIIA, in which X, R₁ andR₃ are as defined under formula I.

The nitroalkanes of formula IIIA can be reduced to the amines of formulaIIA-2, wherein X, R₁ and R₃ are as defined under formula IIIA, by using,for example, LiAlH₄ in an ether solvent, such as diethylether ortetrahydrofurane.

The amines of formula IIA-2 can be chlorinated or brominated, forexample with bromine in the presence of acetic acid, to the amines offormula IIA, wherein Hal is chloro or bromo; and X, R₁ and R₃ are asdefined under formula IIIA.

The halogenated amines of formula IIA can be amidated by using thecorresponding acid derivatives, such as acid chlorides of the formulaA-C(O)Cl, wherein A is as defined under formula I, to form thehalogenated amides of formula IA. Said amidations are convenientlycarried out in the presence of a base, such as triethylamine, Hunigbase, sodium bicarbonate, sodium carbonate, potassium carbonate,pyridine or quinoline, but preferably triethylamine, and in a solvent,such as diethylether, TBME, THF, dichloromethane, chloroform, DMF orNMP, for between 10 minutes and 48 hours, preferably 12 to 24 hours, andbetween 0° C. and reflux, preferably 20 to 25° C.

Compounds of formula I, wherein Q is Q_(1A-1); R₂ and R₄ are bothhydrogen; R_(5a) is chloro or bromo; and R_(5b) is phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl (compounds of formula IA-2 or IA-3 according toscheme 2) may be prepared according to scheme 2.

Compounds of formula IA-2, wherein A, X, R₁ and R₃ are as defined underformula IA and X1 is halogen and q is 0, 1, 2, 3, 4 or 5, may beprepared by reacting an amide of formula IA, wherein A, X, R₁ and R₃ areas defined under formula IA and Hal is bromo with a compound of formulaVII, wherein X1 is halogen and q is 0, 1, 2, 3, 4 or 5, preferably 0 or1, using the well known Suzuki coupling methodology. The Suzuki reactionhas also become one of the standard methods for the direct coupling oftwo aromatic ring systems and is described, for example, in Journal ofthe American Chemical Society 121(41), 9550 (1999) and in Journal fürPraktische Chemie 342(4), 334-339 (2000).

Compounds of the formula IA-3, wherein A, X, R₁ and R₃ are as definedunder formula IA and R* is C₃-C₇ cycloalkyl, phenyl or halogenphenyl,may be prepared reacting an amide of formula IA, wherein A, X, R₁ and R₃are as defined under formula IA and Hal is bromo with an acetynylcompound of the formula VIII, wherein R* is C₃-C₇ cycloalkyl, phenyl orhalogenphenyl, using the well known Sonogashira coupling methodology.The Sonogashira reaction has become one of the standard methods forintroducing an alkynyl function into unsaturated and aromatic orheteroaromatic molecules. It is reviewed, for example, in the Handbookof Organopalladium Chemistry for Organic Synthesis Vol. 1, 767-789(2002); by I. B. Campbell in Organocopper reagents (IRL-Press, 1994); byK. C. Nicolaou et. al. in Angewandte Chemie Int. Ed., 44, 4442 (2005);by R. Tykwinski et. al., ibid. 42, 1433 (2002); and by A. Zapf et.al. inTopics in Catalysis, 19, 101 (2002).

Compounds of formula I, wherein Q is Q_(1B-1); R₂ and R₄ are bothhydrogen; R_(5a) and R_(5b) are both chloro; and R_(5c) is bromo as wellas compounds of formula I, wherein Q is Q_(1B-1); R₂ and R₄ are bothhydrogen; R_(5a) and R_(5c), are both chloro; and R_(5b) is bromo(compounds of formulae IB-1 and IB-2 according to scheme 3a) may beprepared according to scheme 3a.

Thiophene-3-aldehyde (compound of formula VIB) can be exhaustivelychlorinated with Cl₂/AlCl₃ according to known methods to generate thetri-chlorinated thiophene aldehyde of formula VB.

The compound of formula VB can be reacted with a nitroalkane of theformula R₁CH₂NO₂, wherein R₁ is as defined under formula I to form thenitroalkene of formula IVB, in which R₁ is as defined under formula I.

The nitroalkene of the formula IVB can be reacted with a compound of theformula MXR₃, wherein M is Li, Na or K; X and R₃ is as defined underformula I to form the nitroalkanes of formula IIIB, in which X, R₁ andR₃ are as defined under formula I.

The nitroalkanes of formula IIIB can be reduced to the di-chlorinatedamines of formulae IIB-3 and IIB-4, in which X, R₁ and R₃ are as definedunder formula I. Subsequently the amines of formulae IIB-3 and IIB-4 canbe brominated to form the amines of formulae IIB-1 and IIB-2, in whichX, R₁ and R₃ are as defined under formula I.

The brominated amines of formulae IIB-1 and IIB-2 can be amidated byusing the corresponding acid derivatives, such as acid chlorides of theformula A-C(O)Cl, wherein A is as defined under formula I, to form thebrominated amides of formulae IB-1 and IB-2, wherein X, A, R₁ and R₃ areas defined under formula I.

Compounds of formula IB-1 can be prepared according to Scheme 3b:

Compounds of the formulae IB-3 and IB-4

wherein A, X, R₁ and R₃ are as defined under formula IA and X1 ishalogen and q is 0, 1, 2, 3, 4 or 5, may be prepared by reacting thebrominated amines of formulae IB-1 and IB-2 with a compound of formulaVII via the above-described Suzuki reaction.

Compounds of the formulae IB-5 and IB-6

wherein A, X, R₁ and R₃ are as defined under formula IA and R* is C₃-C₇cycloalkyl, phenyl or halogenphenyl, may be prepared by reacting thebrominated amines of formulae IB-1 and IB-2 with an acetynyl compound ofthe formula VIII using the well known Sonogashira coupling methodologyas described above.

Compounds of formulae IIB-1/IIB-2, IIB-3/IIB-4, IB-1/IB-2, IB-3/IB-4 andIB-5/IB-6 can be separated by HPLC.

Compounds of formula I, wherein Q is Q_(2A-1), R_(5a) is chloro; and R₂and R₄ are both hydrogen (compounds of formula IC according to scheme 4)may be prepared according to scheme 4.

Benzthiophenes of formula VC, wherein R_(5b) and R_(5c) are as definedunder formula I, can be prepared from compounds of formula VIC, whereinR_(5b) and R_(5c) are as defined under formula I, as described in J.Org. Chem. 1996, 61(9), 6523-25.

Starting from the benzthiophenes of formula VC, the compounds offormulae IVC, IIIC, IIC and IC, wherein X, A, R₁, R₃, R_(5b) and R_(5c)are as defined under formula I, can be prepared as described above forscheme 1.

Compounds of formula IC, wherein R_(5b) is phenyl, halogenphenyl, C₃-C₇cycloalkyl acetynyl, phenyl acetynyl or halogenphenyl acetynyl; andR_(5c) is hydrogen, may be prepared by reacting a compound of formulaIC, wherein R_(5b) is bromo and R_(5c) is hydrogen, with a compound offormula VII or VIII as described above for scheme 1 via the Suzukireaction or Sonogashira reaction.

The compounds of the formulae VA, VII, VIII, VIB and VIC, wherein thesubstituents as described above, and the compounds of formulae R₁CH₂NO₂and MXR₃, wherein R₁ and R₃ are as defined under formula I; and M is Li,Na or K, are known and commercially available or can be preparedaccording to the above-mentioned references or according to methodsknown in the art.

Compounds of the formula A-C(O)Cl are known and partially commerciallyavailable. They can be prepared analogously as described, for example,in WO 00/09482, WO 02/38542, WO 04/018438, EP-0-589-301, WO 93/11117 andArch. Pharm. Res. 2000, 23(4), 315-323. Compounds of formula I, whereinR₁₅ is C₃-C₇cycloalkyl, can be for example prepared according to thefollowing reaction scheme:

For preparing all further compounds of the formula I functionalizedaccording to the definitions of A, Q, X, R₁, R₂, R₃ and R₄, there are alarge number of suitable known standard methods, such as alkylation,halogenation, acylation, amidation, oximation, oxidation and reduction.The choice of the preparation methods which are suitable are dependingon the properties (reactivity) of the substituents in the intermediates.

The reactions to give compounds of the formula I are advantageouslycarried out in aprotic inert organic solvents. Such solvents arehydrocarbons such as benzene, toluene, xylene or cyclohexane,chlorinated hydrocarbons such as dichloromethane, trichloromethane,tetrachloromethane or chlorobenzene, ethers such as diethyl ether,ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,tetrahydrofuran or dioxane, nitriles such as acetonitrile orpropionitrile, amides such as N,N-dimethylformamide, diethylformamide orN-methylpyrrolidinone. The reaction temperatures are advantageouslybetween −20° C. and +120° C. In general, the reactions are slightlyexothermic and, as a rule, they can be carried out at room temperature.To shorten the reaction time, or else to start the reaction, the mixturemay be heated briefly to the boiling point of the reaction mixture. Thereaction times can also be shortened by adding a few drops of base asreaction catalyst. Suitable bases are, in particular, tertiary aminessuch as trimethylamine, triethylamine, quinuclidine,1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or1,5-diazabicyclo-[5.4.0]undec-7-ene. However, inorganic bases such ashydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g.sodium hydroxide or potassium hydroxide, carbonates such as sodiumcarbonate and potassium carbonate, or hydrogen carbonates such aspotassium hydrogen carbonate and sodium hydrogen carbonate may also beused as bases. The bases can be used as such or else with catalyticamounts of a phase-transfer catalyst, for example a crown ether, inparticular 18-crown-6, or a tetraalkylammonium salt.

The compounds of formula I can be isolated in the customary manner byconcentrating and/or by evaporating the solvent and purified byrecrystallization or trituration of the solid residue in solvents inwhich they are not readily soluble, such as ethers, aromatichydrocarbons or chlorinated hydrocarbons.

The compounds I and, where appropriate, the tautomers thereof, can bepresent in the form of one of the isomers which are possible or as amixture of these, for example in the form of pure isomers, such asantipodes and/or diastereomers, or as isomer mixtures, such asenantiomer mixtures, for example racemates, diastereomer mixtures orracemate mixtures, depending on the number, absolute and relativeconfiguration of asymmetric carbon atoms which occur in the moleculeand/or depending on the configuration of non-aromatic double bonds whichoccur in the molecule; the invention relates to the pure isomers andalso to all isomer mixtures which are possible and is to be understoodin each case in this sense hereinabove and hereinbelow, even whenstereochemical details are not mentioned specifically in each case.

The compounds I and, where appropriate, the tautomers thereof, can, ifappropriate, also be obtained in the form of hydrates and/or includeother solvents, for example those which may have been used for thecrystallization of compounds which are present in solid form.

The intermediates of the formula II

in which Q, X, R₁, R₂, R₃ and R₄ are as defined under formula I, arenovel and were developed specifically for the preparation of thecompounds of the formula I. Accordingly, these intermediates of theformula II also form part of the subject-matter of the presentinvention.

A preferred group of intermediates of the formula II are compounds ofthe formula IIA or IIA-2.

A further preferred group of intermediates of the formula II arecompounds of the formula IIB-1, IIB-2, IIB-3 or IIB-4.

A further preferred group of intermediates of the formula II arecompounds of the formula IIC.

Also the intermediates of the formula III

in which Q, X, R₁, R₂, R₃ and R₄ are as defined under formula I, arenovel and were developed specifically for the preparation of thecompounds of the formula I. Accordingly, these intermediates of theformula III also form part of the subject-matter of the presentinvention.

A preferred group of intermediates of the formula III are compounds ofthe formula IIIA.

A further preferred group of intermediates of the formula III arecompounds of the formula IIIB.

A further preferred group of intermediates of the formula III arecompounds of the formula IIIC.

It has now been found that the compounds of formula I according to theinvention have, for practical purposes, a very advantageous spectrum ofactivities for protecting useful plants against diseases that are causedby phytopathogenic microorganisms, such as fungi, bacteria or viruses.

The invention relates to a method of controlling or preventinginfestation of useful plants by phytopathogenic microorganisms, whereina compound of formula I is applied as active ingredient to the plants,to parts thereof or the locus thereof. The compounds of formula Iaccording to the invention are distinguished by excellent activity atlow rates of application, by being well tolerated by plants and by beingenvironmentally safe. They have very useful curative, preventive andsystemic properties and are used for protecting numerous useful plants.The compounds of formula I can be used to inhibit or destroy thediseases that occur on plants or parts of plants (fruit, blossoms,leaves, stems, tubers, roots) of different crops of useful plants, whileat the same time protecting also those parts of the plants that growlater e.g. from phytopathogenic microorganisms.

It is also possible to use compounds of formula I as dressing agents forthe treatment of plant propagation material, in particular of seeds(fruit, tubers, grains) and plant cuttings (e.g. rice), for theprotection against fungal infections as well as against phytopathogenicfungi occurring in the soil.

Furthermore the compounds of formula I according to the invention may beused for controlling fungi in related areas, for example in theprotection of technical materials, including wood and wood relatedtechnical products, in food storage or in hygiene management.

The compounds of formula I are, for example, effective against thephytopathogenic fungi of the following classes: Fungi imperfecti (e.g.Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercosporaand Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia,Puccinia). Additionally, they are also effective against the Ascomycetesclasses (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula)and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara).Outstanding activity has been observed against powdery mildew (Erysiphespp.). Furthermore, the novel compounds of formula I are effectiveagainst phytopathogenic bacteria and viruses (e.g. against Xanthomonasspp, Pseudomonas spp, Erwinia amylovora as well as against the tobaccomosaic virus). Good activity has been observed against Asian soybeanrust (Phakopsora pachyrhizi).

Within the scope of the invention, useful plants to be protectedtypically comprise the following species of plants: cereal (wheat,barley, rye, oat, rice, maize, sorghum and related species); beet (sugarbeet and fodder beet); pomes, drupes and soft fruit (apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries andblackberries); leguminous plants (beans, lentils, peas, soybeans); oilplants (rape, mustard, poppy, olives, sunflowers, coconut, castor oilplants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers,melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges,lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae(avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee,eggplants, sugar cane, tea, pepper, vines, hops, bananas and naturalrubber plants, as well as ornamentals.

The term “useful plants” is to be understood as including also usefulplants that have been rendered tolerant to herbicides like bromoxynil orclasses of herbicides (such as, for example, HPPD inhibitors, ALSinhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron,EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)inhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant toimidazolinones, e.g. imazamox, by conventional methods of breeding(mutagenesis) is Clearfield® summer rape (Canola). Examples of cropsthat have been rendered tolerant to herbicides or classes of herbicidesby genetic engineering methods include glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising one or more selectivelyacting toxins, such as are known, for example, from toxin-producingbacteria, especially those of the genus Bacillus.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising antipathogenicsubstances having a selective action, such as, for example, theso-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392225). Examples of such antipathogenic substances and transgenic plantscapable of synthesising such antipathogenic substances are known, forexample, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. Themethods of producing such transgenic plants are generally known to theperson skilled in the art and are described, for example, in thepublications mentioned above.

The term “locus” of a useful plant as used herein is intended to embracethe place on which the useful plants are growing, where the plantpropagation materials of the useful plants are sown or where the plantpropagation materials of the useful plants will be placed into the soil.An example for such a locus is a field, on which crop plants aregrowing.

The term “plant propagation material” is understood to denote generativeparts of the plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

The compounds of formula I can be used in unmodified form or,preferably, together with carriers and adjuvants conventionally employedin the art of formulation.

Therefore the invention also relates to compositions for controlling andprotecting against phytopathogenic microorganisms, comprising a compoundof formula I and an inert carrier, and to a method of controlling orpreventing infestation of useful plants by phytopathogenicmicroorganisms, wherein a composition, comprising a compound of formulaI as acitve ingredient and an inert carrier, is applied to the plants,to parts thereof or the locus thereof.

To this end compounds of formula I and inert carriers are convenientlyformulated in known manner to emulsifiable concentrates, coatablepastes, directly sprayable or dilutable solutions, dilute emulsions,wettable powders, soluble powders, dusts, granulates, and alsoencapsulations e.g. in polymeric substances. As with the type of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering, coating or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances. Thecompositions may also contain further adjuvants such as stabilizers,antifoams, viscosity regulators, binders or tackifiers as well asfertilizers, micronutrient donors or other formulations for obtainingspecial effects.

Suitable carriers and adjuvants can be solid or liquid and aresubstances useful in formulation technology, e.g. natural or regeneratedmineral substances, solvents, dispersants, wetting agents, tackifiers,thickeners, binders or fertilizers. Such carriers are for exampledescribed in WO 97/33890.

The compounds of formula I or compositions, comprising a compound offormula I as acitve ingredient and an inert carrier, can be applied tothe locus of the plant or plant to be treated, simultaneously or insuccession with further compounds. These further compounds can be e.g.fertilizers or micronutrient donors or other preparations whichinfluence the growth of plants. They can also be selective herbicides aswell as insecticides, fungicides, bactericides, nematicides,molluscicides or mixtures of several of these preparations, if desiredtogether with further carriers, surfactants or application promotingadjuvants customarily employed in the art of formulation.

A preferred method of applying a compound of formula I, or acomposition, comprising a compound of formula I as active ingredient andan inert carrier, is foliar application. The frequency of applicationand the rate of application will depend on the risk of infestation bythe corresponding pathogen. However, the compounds of formula I can alsopenetrate the plant through the roots via the soil (systemic action) bydrenching the locus of the plant with a liquid formulation, or byapplying the compounds in solid form to the soil, e.g. in granular form(soil application). In crops of water rice such granulates can beapplied to the flooded rice field. The compounds of formula I may alsobe applied to seeds (coating) by impregnating the seeds or tubers eitherwith a liquid formulation of the fungicide or coating them with a solidformulation.

A formulation, i.e. a composition comprising the compound of formula Iand, if desired, a solid or liquid adjuvant, is prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally,surface-active compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% byweight, preferably from 0.1 to 95% by weight, of the compound of formulaI, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid orliquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25%by weight, of a surfactant.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

Advantageous rates of application are normally from 5 g to 2 kg ofactive ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kga.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seeddrenching agent, convenient rates of application are from 10 mg to 1 gof active substance per kg of seeds. The rate of application for thedesired action can be determined by experiments. It depends for exampleon the type of action, the developmental stage of the useful plant, andon the application (location, timing, application method) and can, owingto these parameters, vary within wide limits.

Surprisingly, it has now been found that the compounds of formula I canalso be used in methods of protecting crops of useful plants againstattack by phytopathogenic organisms as well as the treatment of crops ofuseful plants infested by phytopathogenic organisms comprisingadministering a combination of glyphosate and at least one compound offormula I to the plant or locus thereof, wherein the plant is resistantor sensitive to glyphosate.

Said methods may provide unexpectedly improved control of diseasescompared to using the compounds of formula I in the absence ofglyphosate. Said methods may be effective at enhancing the control ofdisease by compounds of formula I. While the mixture of glyphosate andat least one compound of formula I may increase the disease spectrumcontrolled, at least in part, by the compound of formula I, an increasein the activity of the compound of formula I on disease species alreadyknown to be controlled to some degree by the compound of formula I canalso be the effect observed.

Said methods are particularly effective against the phytopathogenicorganisms of the kingdom Fungi, phylum Basidiomycot, classUredinomycetes, subclass Urediniomycetidae and the order Uredinales(commonly referred to as rusts). Species of rusts having a particularlylarge impact on agriculture include those of the family Phakopsoraceae,particularly those of the genus Phakopsora, for example Phakopsorapachyrhizi, which is also referred to as Asian soybean rust, and thoseof the family Pucciniaceae, particularly those of the genus Pucciniasuch as Puccinia graminis, also known as stem rust or black rust, whichis a problem disease in cereal crops and Puccinia recondita, also knownas brown rust.

An embodiment of said method is a method of protecting crops of usefulplants against attack by a phytopathogenic organism and/or the treatmentof crops of useful plants infested by a phytopathogenic organism, saidmethod comprising simultaneously applying glyphosate, including salts oresters thereof, and at least one compound of formula I, which hasactivity against the phytopathogenic organism to at least one memberselected from the group consisting of the plant, a part of the plant andthe locus of the plant.

The compounds of formula (I), or a pharmaceutical salt thereof,described above may also have an advantageous spectrum of activity forthe treatment and/or prevention of microbial infection in an animal.

“Animal” can be any animal, for example, insect, mammal, reptile, fish,amphibian, preferably mammal, most preferably human. “Treatment” meansthe use on an animal which has microbial infection in order to reduce orslow or stop the increase or spread of the infection, or to reduce theinfection or to cure the infection. “Prevention” means the use on ananimal which has no apparent signs of microbial infection in order toprevent any future infection, or to reduce or slow the increase orspread of any future infection. According to the present invention thereis provided the use of a compound of formula (I) in the manufacture of amedicament for use in the treatment and/or prevention of microbialinfection in an animal. There is also provided the use of a compound offormula (I) as a pharmaceutical agent. There is also provided the use ofa compound of formula (I) as an antimicrobial agent in the treatment ofan animal. According to the present invention there is also provided apharmaceutical composition comprising as an active ingredient a compoundof formula (I), or a pharmaceutically acceptable salt thereof, and apharmaceutically acceptable diluent or carrier. This composition can beused for the treatment and/or prevention of antimicrobial infection inan animal. This pharmaceutical composition can be in a form suitable fororal administration, such as tablet, lozenges, hard capsules, aqueoussuspensions, oily suspensions, emulsions dispersible powders,dispersible granules, syrups and elixirs. Alternatively thispharmaceutical composition can be in a form suitable for topicalapplication, such as a spray, a cream or lotion. Alternatively thispharmaceutical composition can be in a form suitable for parenteraladministration, for example injection. Alternatively this pharmaceuticalcomposition can be in inhalable form, such as an aerosol spray.

The compounds of formula (I) may be effective against various microbialspecies able to cause a microbial infection in an animal. Examples ofsuch microbial species are those causing Aspergillosis such asAspergillus fumigatus, A. flavus, A. terrus, A. nidulans and A. niger,those causing Blastomycosis such as Blastomyces dermatitidis; thosecausing Candidiasis such as Candida albicans, C. glabrata, C.tropicalis, C. parapsilosis, C. krusei and C. lusitaniae; those causingCoccidioidomycosis such as Coccidioides immitis; those causingCryptococcosis such as Cryptococcus neoformans; those causingHistoplasmosis such as Histoplasma capsulatum and those causingZygomycosis such as Absidia cotymbifera, Rhizomucor pusillus andRhizopus arrhizus. Further examples are Fusarium Spp such as Fusariumoxysporum and Fusarium solani and Scedosporium Spp such as Scedosporiumapiospermum and Scedosporium prolificans. Still further examples areMicrosporum Spp, Trichophyton Spp, Epidermophyton Spp, Mucor Spp,Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp,Paracoccidioides Spp and Histoplasma Spp.

The following non-limiting Examples illustrate the above-describedinvention in greater detail without limiting it.

PREPARATION EXAMPLES Example P1 Preparation of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid[2-(3,5-dichlorobenzo[b]thiophen-2-yl)-2-methoxy-1-methylethyl]amide(compound 22.2)

In a sulfonation flask 0.2 g (0.68 mmol) of the amine prepared inexample P2c) and 83 mg (0.82 mmol) triethylamine are dissolved in 10 mlof methylenechloride. Then a mixture of 132 mg (0.68 mmol)3-difluoromethyl-1-methyl-1-H-pyrazole 4-carboxylic acid chloride and 8ml methylenechloride is added at room temperature under stirring. Afterstirring for 16 hours the solvent is evaporated in a water jet vacuumand the residue purified by column chromatography over silicagel(eluent: ethylacetate/hexane 1:1). Yield: 240 mg white crystals (80% oftheory); m.p. 128-132° C.

Example P2 Preparation of2-(3,5-dichlorobenz[b]thiophene-2-yl)-2-methoxy-1-methylethylamine a)Preparation of 3,5-dichloro-2-((E)-nitropropenyl)benzo[b]thiophene

In a sulfonation flask, a mixture containing 6.93 g (0.03 mol)3,5-dichlorobenzo[b]thio-phene-2-carbaldehyde, 18 g (0.24 mol)nitroethane, 5.8 g (0.075 mol) ammoniumacetate and 60 ml acetic acid isheated at 90° C. for 6 hours. After cooling ethylacetate is added andthe organic phase washed three times with water. The organic phase isdried over sodium sulphate and after filration the organic solvent isdistilled off in a water jet vacuum. The residue is purified by columnchromatography over silicagel (eluent: ethylacetate/heptane 1:5). Afterchromatography further purification via crystallisation fromethylacetate could be achieved. Yield: 4 g (47% of theory). M.p.143°-146° C.

b) Preparation of3,5-dichloro-2-(1-methoxy-2-nitropropyl)benzo[b]thiophene (compoundZ6.2)

In a sulfonation flask 0.89 g (0.003 mol)3.5-dichloro-2-((E/Z)-nitropropenyl)benzo[b]thiophene is dissolved in 30ml of toluene. Then a solution of 2.3 ml of 5.4 m (0.00124 mol)methanolate solution is diluted with 4 ml of methanol and added dropwiseto the nitroolefine under stirring at room temperature. The mixture isstirred 3 hours at rt and then 3 ml acetic acid are added and stirringcontinued for 30 minutes. Then water was added and stirring contued fora few minutes. After addition of ethylacetate the organic phase isseparated and the solvent distilled off in a water jet vacuum. Theobtained raw material could be used in the next step without furtherpurification. Yield: 1.0 g (ca. 100% of theory) in form of a yellowishoil (diastereoisomeric mixture, ratio: 3:2). ¹H-NMR: 1.45/d/3H-DS1(minor isomer), 1.65/d/3H-DS2 (major isomer), 3.30/s/3H-DS1,3.46/s/3H-DS2, 4.82/m/1H-DS2, 4.87/m/1H-DS1, 5.3/d/1H-DS1,5.48/d/1H-DS2, 7.4/m/2H-DS1+DS2, 7.7-7.85/m/4H-DS1+DS2.

c) Preparation of2-(3,5-dichlorobenz[b]thiophene-2-yl)-2-methoxy-1-methylethylamine(compound Z3.2)

In a sulfonation flask 15 ml (0.015 mol) of an etheral 1 molar LiAlH₄solution is diluted with 40 ml of diethylether. A solution of 0.97 g(0.003 mol) 3,5-dichloro-2-(1-methoxy-2-nitropropyl)benzo[b]thiopheneand 30 ml diethylether is added under stirring in such a manner that theinternal temperature remains constant at 0-5° C. Then the mixture iswarmed up to it and stirring continued for 5 h. Then the reactionmixture is cooled again and water added slowly. After quenching sodiumsulphate is added. Filtration and distilling off the solvent in a waterjet vacuum, the raw material is obtained. Purification is achieved bycolumn chromatography (eluent: tert. butylmethylether/EtOH 3:1). Yield:0.62 g (87% of theory) yellowish oil consisting of a diastereoisomericmixture (ratio:ca. 2:1). ¹H-NMR: 1.05/d/3H-DS1 (minor isomer),1.13/d/3H, DS2 (major isomer), 3.2/m/1H-DS1, 3.35/s/6H-DS1+DS2,3.39/m/1H-DS2, 4.45/d/1H-DS1, 4.52/d/1H-DS2, 7.38/m/2H-DS1+DS2,7.72/d/2H-DS1+DS2, 7.8/2 s/DS1+DS2.

Tables 1 to 13: Compounds of Formula I-1

The invention is further illustrated by the preferred individualcompounds of formula (I-1) listed below in Tables 1 to 13.Characterising data is given in Table 40.

Each of Tables 1 to 13, which follow the Table V below, comprises 48compounds of the formula (I-1) in which R₁, X—R₃, R_(5a), R_(5b) andR_(5c) have the values given in Table V and A has the value given in therelevant Table 1 to 13. Thus Table 1 corresponds to Table V when V is 1and A has the value given under the Table 1 heading, Table 2 correspondsto Table V when V is 2 and A has the value given under the Table 2heading, and so on for Tables 3 to 13.

TABLE V Compound Number R₁ XR₃ R_(5a) R_(5b) R_(5c) V.1 H OMe Cl Cl HV.2 Me OMe Cl Cl H V.3 H OMe Cl Br H V.4 Me OMe Cl Br H V.5 H OEt Cl ClH V.6 Me OEt Cl Cl H V.7 H OEt Cl Br H V.8 Me OEt Cl Br H V.9 H SMe ClCl H V.10 Me SMe Cl Cl H V.11 H SMe Cl Br H V.12 Me SMe Cl Br H V.13 HSEt Cl Cl H V.14 Me SEt Cl Cl H V.15 H SEt Cl Br H V.16 Me SEt Cl Br HV.17 H OMe Cl

H V.18 Me OMe Cl

H V.19 H OEt Cl

H V.20 Me OEt Cl

H V.21 H OMe Cl

H V.22 Me OMe Cl

H V.23 H OEt Cl

H V.24 Me OEt Cl

H V.25 H OMe Cl

H V.26 Me OMe Cl

H V.27 H OEt Cl

H V.28 Me OEt Cl

H V.29 H OMe Cl

H V.30 Me OMe Cl

H V.31 H OEt Cl

H V.32 Me OEt Cl

H V.33 H OMe Cl

H V.34 Me OMe Cl

H V.35 H OEt Cl

H V.36 Me OEt Cl

H V.37 H OMe Cl

H V.38 Me OMe Cl

H V.39 H OEt Cl

H V.40 Me OEt Cl

H V.41 H OMe Cl H H V.42 Me OMe Cl H H V.43 H OEt Cl H H V.44 Me OEt ClH H V.45 H SMe Cl H H V.46 Me SMe Cl H H V.47 H SEt Cl H H V.48 Me SEtCl H H

Table 1 provides 48 compounds of formula (I-1), wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V. For example, compound 1.1 has the followingstructure:

Table 2 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 3 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 4 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 5 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 6 provides 48 compounds of formula (I-1) wherein. A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 7 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 8 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 9 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 10 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 11 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Table 12 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c), are asdefined in Table V.

Table 13 provides 48 compounds of formula (I-1) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table V.

Tables 14 to 20: Compounds of Formula I-2:

The invention is further illustrated by the preferred individualcompounds of formula (I-2) listed below in Tables 14 to 20.Characterising data is given in Table 40.

Each of Tables 14 to 20, which follow the Table W below, comprises 158compounds of the formula (I-2) in which R₁, X—R₃, R_(5a), R_(5b) andR_(5c) have the values given in Table W and A has the value given in therelevant Table 14 to 20. Thus Table 14 corresponds to Table W when W is14 and A has the value given under the Table 14 heading, Table 15corresponds to Table W when W is 15 and A has the value given under theTable 15 heading, and so on for Tables 16 to 20.

TABLE W Com - pound Num- ber R₁ XR₃ R_(5a) R_(5b) R_(5c) W.1 H OMe Cl

Cl W.2 Me OMe Cl

Cl W.3 H OEt Cl

Cl W.4 Me OEt Cl

Cl W.5 H SMe Cl

Cl W.6 Me SMe Cl

Cl W.7 H SEt Cl

Cl W.8 Me SEt Cl

Cl W.9 H OMe Cl Cl

W.10 Me OMe Cl Cl

W.11 H OEt Cl Cl

W.12 Me OEt Cl Cl

W.13 H SMe Cl Cl

W.14 Me SMe Cl Cl

W.15 H SEt Cl Cl

W.16 Me SEt Cl Cl

W.17 H OMe Cl

Cl W.18 Me OMe Cl

Cl W.19 H OEt Cl

Cl W.20 Me OEt Cl

Cl W.21 H SMe Cl

Cl W.22 Me SMe Cl

Cl W.23 H SEt Cl

Cl W.24 Me SEt Cl

Cl W.25 H OMe Cl Cl

W.26 Me OMe Cl Cl

W.27 H OEt Cl Cl

W.28 Me OEt Cl Cl

W.29 H SMe Cl Cl

W.30 Me SMe Cl Cl

W.31 H SEt Cl Cl

W.32 Me SEt Cl Cl

W.33 H OMe Cl

Cl W.34 Me OMe Cl

Cl W.35 H OEt Cl

Cl W.36 Me OEt Cl

Cl W.37 H SMe Cl

Cl W.38 Me SMe Cl

Cl W.39 H SEt Cl

Cl W.40 Me SEt Cl

Cl W.41 H OMe Cl Cl

W.42 Me OMe Cl Cl

W.43 H OEt Cl Cl

W.44 Me OEt Cl Cl

W.45 H SMe Cl Cl

W.46 Me SMe Cl Cl

W.47 H SEt Cl Cl

W.48 Me SEt Cl Cl

W.49 H OMe Cl

Cl W.50 Me OMe Cl

Cl W.51 H OEt Cl

Cl W.52 Me OEt Cl

Cl W.53 H SMe Cl

Cl W.54 Me SMe Cl

Cl W.55 H SEt Cl

Cl W.56 Me SEt Cl

Cl W.57 H OMe Cl Cl

W.58 Me OMe Cl Cl

W.59 H OEt Cl Cl

W.60 Me OEt Cl Cl

W.61 H SMe Cl Cl

W.62 Me SMe Cl Cl

W.63 H SEt Cl Cl

W.64 Me SEt Cl Cl

W.65 H OMe Cl

Cl W.66 Me OMe Cl

Cl W.67 H OEt Cl

Cl W.68 Me OEt Cl

Cl W.69 H SMe Cl

Cl W.70 Me SMe Cl

Cl W.71 H SEt Cl

Cl W.72 Me SEt Cl

Cl W.73 H OMe Cl Cl

W.74 Me OMe Cl Cl

W.75 H OEt Cl Cl

W.76 Me OEt Cl Cl

W.77 H SMe Cl Cl

W.78 Me SMe Cl Cl

W.79 H SEt Cl Cl

W.80 Me SEt Cl Cl

W.81 H OMe Cl

Cl W.82 Me OMe Cl

Cl W.83 H OEt Cl

Cl W.84 Me OEt Cl

W.85 H SMe Cl

Cl W.86 Me SMe Cl

Cl W.87 H SEt Cl

Cl W.88 Me SEt Cl

Cl W.89 H OMe Cl Cl

W.90 Me OMe Cl Cl

W.91 H OEt Cl Cl

W.92 Me OEt Cl Cl

W.93 H SMe Cl Cl

W.94 Me SMe Cl Cl

W.95 H SEt Cl Cl

W.96 Me SEt Cl Cl

W.97 H OMe Cl Cl Cl W.98 Me OMe Cl Cl Cl W.99 H OEt Cl Cl Cl W.100 MeOEt Cl Cl Cl W.101 H SMe Cl Cl Cl W.102 Me SMe Cl Cl Cl W.103 H SEt ClCl Cl W.104 Me SEt Cl Cl Cl W.105 H OMe Cl H Cl W.106 Me OMe Cl H ClW.107 H OEt Cl H Cl W.108 Me OEt Cl H Cl W.109 H SMe Cl H Cl W.110 MeSMe Cl H Cl W.111 H SEt Cl H Cl W.112 Me SEt Cl H Cl W.113 H OMe Cl Cl HW.114 Me OMe Cl Cl H W.115 H OEt Cl Cl H W.116 Me OEt Cl Cl H W.117 HSMe Cl Cl H W.118 Me SMe Cl Cl H W.119 H SEt Cl Cl H W.120 Me SEt Cl ClH W.121 H OMe Cl Br Cl W.122 Me OMe Cl Br Cl W.123 H OEt Cl Br Cl W.124Me OEt Cl Br Cl W.125 H SMe Cl Br Cl W.126 Me SMe Cl Br Cl W.127 H SEtCl Br Cl W.128 Me SEt Cl Br Cl W.129 H OMe Cl Cl Br W.130 Me OMe Cl ClBr W.131 H OEt Cl Cl Br W.132 Me OEt Cl Cl Br W.133 H SMe Cl Cl Br W.134Me SMe Cl Cl Br W.135 H SEt Cl Cl Br W.136 Me SEt Cl Cl Br W.137 H OMeCl Cl

W.138 Me OMe Cl Cl

W.139 H OMe Cl Cl

W.140 Me OMe Cl Cl

W.141 H OMe Cl Cl

W.142 Me OMe Cl Cl

W.143 H OMe Cl Cl

W.144 Me OMe Cl Cl

W.145 H OMe Cl Cl

W.146 Me OMe Cl Cl

W.147 H OMe Cl Cl

W.148 Me OMe Cl Cl

W.149 H OMe Cl Cl

W.150 Me OMe Cl Cl

W.151 H OMe Cl Cl

W.152 Me OMe Cl Cl

W.153 H OMe Cl Cl

W.154 Me OMe Cl Cl

W.155 H OMe Cl Cl

W.156 Me OMe Cl Cl

W.157 H OMe Cl Cl

W.158 Me OMe Cl Cl

Table 14 provides 158 compounds of formula (I-2), wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table W.

Table 15 provides 158 compounds of formula (I-2) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table W.

Table 16 provides 158 compounds of formula (I-2) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table W.

Table 17 provides 158 compounds of formula (I-2) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table W.

Table 18 provides 158 compounds of formula (I-2) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table W.

Table 19 provides 158 compounds of formula (I-2) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table W.

Table 20 provides 158 compounds of formula (I-2) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table W.

Tables 21 to 33: Compounds of Formula I-3:

The invention is further illustrated by the preferred individualcompounds of formula (I-3) listed below in Tables 21 to 33.Characterising data is given in Table 40.

Each of Tables 21 to 33, which follow the Table Y below, comprises 64compounds of the formula (I-3) in which R₁, X—R₃, R_(5a), R_(5b) andR_(5c) have the values given in Table Y and A has the value given in therelevant Table 21 to 33. Thus Table 21 corresponds to Table Y when Y is21 and A has the value given under the Table 21 heading, Table 22corresponds to Table Y when Y is 22 and A has the value given under theTable 22 heading, and so on for Tables 23 to 33.

TABLE Y Compound Number R₁ XR₃ R_(5a) R_(5b) R_(5c) Y.1 H OMe Cl 5′-Cl HY.2 Me OMe Cl 5′-Cl H Y.3 H OEt Cl 5′-Cl H Y.4 Me OEt Cl 5′-Cl H Y.5 HSMe Cl 5′-Cl H Y.6 Me SMe Cl 5′-Cl H Y.7 H SEt Cl 5′-Cl H Y.8 Me SEt Cl5′-Cl H Y.9 H OMe Cl 5′-Br H Y.10 Me OMe Cl 5′-Br H Y.11 H OEt Cl 5′-BrH Y.12 Me OEt Cl 5′-Br H Y.13 H SMe Cl 5′-Br H Y.14 Me SMe Cl 5′-Br HY.15 H SEt Cl 5′-Br H Y.16 Me SEt Cl 5′-Br H Y.17 H OMe Cl

H Y.18 Me OMe Cl

H Y.19 H OEt Cl

H Y.20 Me OEt Cl

H Y.21 H SMe Cl

H Y.22 Me SMe Cl

H Y.23 H SEt Cl

H Y.24 Me SEt Cl

H Y.25 H OMe Cl

H Y.26 Me OMe Cl

H Y.27 H OEt Cl

H Y.28 Me OEt Cl

H Y.29 H SMe Cl

H Y.30 Me SMe Cl

H Y.31 H SEt Cl

H Y.32 Me SEt Cl

H Y.33 H OMe Cl 6′-Cl H Y.34 Me OMe Cl 6′-Cl H Y.35 H OEt Cl 6′-Cl HY.36 Me OEt Cl 6′-Cl H Y.37 H SMe Cl 6′-Cl H Y.38 Me SMe Cl 6′-Cl H Y.39H SEt Cl 6′-Cl H Y.40 Me SEt Cl 6′-Cl H Y.41 H OMe Cl 6′-Br H Y.42 MeOMe Cl 6′-Br H Y.43 H OEt Cl 6′-Br H Y.44 Me OEt Cl 6′-Br H Y.45 H SMeCl 6′-Br H Y.46 Me SMe Cl 6′-Br H Y.47 H SEt Cl 6′-Br H Y.48 Me SEt Cl6′-Br H Y.49 H OMe Cl

H Y.50 Me OMe Cl

H Y.51 H OEt Cl

H Y.52 Me OEt Cl

H Y.53 H SMe Cl

H Y.54 Me SMe Cl

H Y.55 H SEt Cl

H Y.56 Me SEt Cl

H Y.57 H OMe Cl

H Y.58 Me OMe Cl

H Y.59 H OEt Cl

H Y.60 Me OEt Cl

H Y.61 H SMe Cl

H Y.62 Me SMe Cl

H Y.63 H SEt Cl

H Y.64 Me SEt Cl

H

Table 21 provides 64 compounds of formula (I-3), wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 22 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 23 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 24 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 25 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table.

Table 26 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 27 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 28 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 29 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 30 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 31 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table.

Table 32 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

Table 33 provides 64 compounds of formula (I-3) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Y.

TABLE 34 Compounds of formula II-1 The invention is further illustratedby the preferred individual compounds of formula (II-1) listed below inTable 34. Characterising data is given in Table 40. (II-1)

Compound Number R₁ XR₃ R_(5a) R_(5b) R_(5c) Z1.1 H OMe Cl Cl H Z1.2 MeOMe Cl Cl H Z1.3 H OMe Cl Br H Z1.4 Me OMe Cl Br H Z1.5 H OEt Cl Cl HZ1.6 Me OEt Cl Cl H Z1.7 H OEt Cl Br H Z1.8 Me OEt Cl Br H Z1.9 H SMe ClCl H Z1.10 Me SMe Cl Cl H Z1.11 H SMe Cl Br H Z1.12 Me SMe Cl Br H Z1.13H SEt Cl Cl H Z1.14 Me SEt Cl Cl H Z1.15 H SEt Cl Br H Z1.16 Me SEt ClBr H Z1.17 H OMe Cl

H Z1.18 Me OMe Cl

H Z1.19 H OEt Cl

H Z1.20 Me OEt Cl

H Z1.21 H OMe Cl

H Z1.22 Me OMe Cl

H Z1.23 H OEt Cl

H Z1.24 Me OEt Cl

H Z1.25 H OMe Cl

H Z1.26 Me OMe Cl

H Z1.27 H OEt Cl

H Z1.28 Me OEt Cl

H Z1.29 H OMe Cl

H Z1.30 Me OMe Cl

H Z1.31 H OEt Cl

H Z1.32 Me OEt Cl

H Z1.33 H OMe Cl

H Z1.34 Me OMe Cl

H Z1.35 H OEt Cl

H Z1.36 Me OEt Cl

H Z1.37 H OMe Cl

H Z1.38 Me OMe Cl

H Z1.39 H OEt Cl

H Z1.40 Me OEt Cl

H Z1.41 H OMe Cl H H Z1.42 Me OMe Cl H H Z1.43 H OEt Cl H H Z1.44 Me OEtCl H H Z1.45 H SMe Cl H H Z1.46 Me SMe Cl H H Z1.47 H SEt Cl H H Z1.48Me SEt Cl H H

TABLE 35 Compounds of formula II-2 The invention is further illustratedby the preferred individual compounds of formula (II-2) listed below inTable 35. Characterising data is given in Table 40. (II-2)

Com- pound Num- ber R₁ XR₃ R_(5a) R_(5b) R_(5c) Z2.1 H OMe Cl

Cl Z2.2 Me OMe Cl

Cl Z2.3 H OEt Cl

Cl Z2.4 Me OEt Cl

Cl Z2.5 H SMe Cl

Cl Z2.6 Me SMe Cl

Cl Z2.7 H SEt Cl

Cl Z2.8 Me SEt Cl

Cl Z2.9 H OMe Cl Cl

Z2.10 Me OMe Cl Cl

Z2.11 H OEt Cl Cl

Z2.12 Me OEt Cl Cl

Z2.13 H SMe Cl Cl

Z2.14 Me SMe Cl Cl

Z2.15 H SEt Cl Cl

Z2.16 Me SEt Cl Cl

Z2.17 H OMe Cl

Cl Z2.18 Me OMe Cl

Cl Z2.19 H OEt Cl

Cl Z2.20 Me OEt Cl

Cl Z2.21 H SMe Cl

Cl Z2.22 Me SMe Cl

Cl Z2.23 H SEt Cl

Cl Z2.24 Me SEt Cl

Cl Z2.25 H OMe Cl Cl

Z2.26 Me OMe Cl Cl

Z2.27 H OEt Cl Cl

Z2.28 Me OEt Cl Cl

Z2.29 H SMe Cl Cl

Z2.30 Me SMe Cl Cl

Z2.31 H SEt Cl Cl

Z2.32 Me SEt Cl Cl

Z2.33 H OMe Cl

Cl Z2.34 Me OMe Cl

Cl Z2.35 H OEt Cl

Cl Z2.36 Me OEt Cl

Cl Z2.37 H SMe Cl

Cl Z2.38 Me SMe Cl

Cl Z2.39 H SEt Cl

Cl Z2.40 Me SEt Cl

Cl Z2.41 H OMe Cl Cl

Z2.42 Me OMe Cl Cl

Z2.43 H OEt Cl Cl

Z2.44 Me OEt Cl Cl

Z2.45 H SMe Cl Cl

Z2.46 Me SMe Cl Cl

Z2.47 H SEt Cl Cl

Z2.48 Me SEt Cl Cl

Z2.49 H OMe Cl

Cl Z2.50 Me OMe Cl

Cl Z2.51 H OEt Cl

Cl Z2.52 Me OEt Cl

Cl Z2.53 H SMe Cl

Cl Z2.54 Me SMe Cl

Cl Z2.55 H SEt Cl

Cl Z2.56 Me SEt Cl

Cl Z2.57 H OMe Cl Cl

Z2.58 Me OMe Cl Cl

Z2.59 H OEt Cl Cl

Z2.60 Me OEt Cl Cl

Z2.61 H SMe Cl Cl

Z2.62 Me SMe Cl Cl

Z2.63 H SEt Cl Cl

Z2.64 Me SEt Cl Cl

Z2.65 H OMe Cl

Cl Z2.66 Me OMe Cl

Cl Z2.67 H OEt Cl

Cl Z2.68 Me OEt Cl

Cl Z2.69 H SMe Cl

Cl Z2.70 Me SMe Cl

Cl Z2.71 H SEt Cl

Cl Z2.72 Me SEt Cl

Cl Z2.73 H OMe Cl Cl

Z2.74 Me OMe Cl Cl

Z2.75 H OEt Cl Cl

Z2.76 Me OEt Cl Cl

Z2.77 H SMe Cl Cl

Z2.78 Me SMe Cl Cl

Z2.79 H SEt Cl Cl

Z2.80 Me SEt Cl Cl

Z2.81 H OMe Cl

Cl Z2.82 Me OMe Cl

Cl Z2.83 H OEt Cl

Cl Z2.84 Me OEt Cl

Cl Z2.85 H SMe Cl

Cl Z2.86 Me SMe Cl

Cl Z2.87 H SEt Cl

Cl Z2.88 Me SEt Cl

Cl Z2.89 H OMe Cl Cl

Z2.90 Me OMe Cl Cl

Z2.91 H OEt Cl Cl

Z2.92 Me OEt Cl Cl

Z2.93 H SMe Cl Cl

Z2.94 Me SMe Cl Cl

Z2.95 H SEt Cl Cl

Z2.96 Me SEt Cl Cl

Z2.97 H OMe Cl Cl Cl Z2.98 Me OMe Cl Cl Cl Z2.99 H OEt Cl Cl Cl Z2.100Me OEt Cl Cl Cl Z2.101 H SMe Cl Cl Cl Z2.102 Me SMe Cl Cl Cl Z2.103 HSEt Cl Cl Cl Z2.104 Me SEt Cl Cl Cl Z2.105 H OMe Cl H Cl Z2.106 Me OMeCl H Cl Z2.107 H OEt Cl H Cl Z2.108 Me OEt Cl H Cl Z2.109 H SMe Cl H ClZ2.110 Me SMe Cl H Cl Z2.111 H SEt Cl H Cl Z2.112 Me SEt Cl H Cl Z2.113H OMe Cl Cl H Z2.114 Me OMe Cl Cl H Z2.115 H OEt Cl Cl H Z2.116 Me OEtCl Cl H Z2.117 H SMe Cl Cl H Z2.118 Me SMe Cl Cl H Z2.119 H SEt Cl Cl HZ2.120 Me SEt Cl Cl H Z2.121 H OMe Cl Br Cl Z2.122 Me OMe Cl Br ClZ2.123 H OEt Cl Br Cl Z2.124 Me OEt Cl Br Cl Z2.125 H SMe Cl Br ClZ2.126 Me SMe Cl Br Cl Z2.127 H SEt Cl Br Cl Z2.128 Me SEt Cl Br ClZ2.129 H OMe Cl Cl Br Z2.130 Me OMe Cl Cl Br Z2.131 H OEt Cl Cl BrZ2.132 Me OEt Cl Cl Br Z2.133 H SMe Cl Cl Br Z2.134 Me SMe Cl Cl BrZ2.135 H SEt Cl Cl Br Z2.136 Me SEt Cl Cl Br

TABLE 36 Compounds of formula II-3 The invention is further illustratedby the preferred individual compounds of formula (II-3) listed below inTable 36. Characterising data is given in Table 40. (II-3)

Com- pound Num- ber R₁ XR₃ R_(5a) R_(5b) R_(5c) Z3.1 H OMe Cl 5′-Cl HZ3.2 Me OMe Cl 5′-Cl H Z3.3 H OEt Cl 5′-Cl H Z3.4 Me OEt Cl 5′-Cl H Z3.5H SMe Cl 5′-Cl H Z3.6 Me SMe Cl 5′-Cl H Z3.7 H SEt Cl 5′-Cl H Z3.8 MeSEt Cl 5′-Cl H Z3.9 H OMe Cl 5′-Br H Z3.10 Me OMe Cl 5′-Br H Z3.11 H OEtCl 5′-Br H Z3.12 Me OEt Cl 5′-Br H Z3.13 H SMe Cl 5′-Br H Z3.14 Me SMeCl 5′-Br H Z3.15 H SEt Cl 5′-Br H Z3.16 Me SEt Cl 5′-Br H Z3.17 H OMe Cl

H Z3.18 Me OMe Cl

H Z3.19 H OEt Cl

H Z3.20 Me OEt Cl

H Z3.21 H SMe Cl

H Z3.22 Me SMe Cl

H Z3.23 H SEt Cl

H Z3.24 Me SEt Cl

H Z3.25 H OMe Cl

H Z3.26 Me OMe Cl

H Z3.27 H OEt Cl

H Z3.28 Me OEt Cl

H Z3.29 H SMe Cl

H Z3.30 Me SMe Cl

H Z3.31 H SEt Cl

H Z3.32 Me SEt Cl

H Z3.33 H OMe Cl 6′-Cl H Z3.34 Me OMe Cl 6′-Cl H Z3.35 H OEt Cl 6′-Cl HZ3.36 Me OEt Cl 6′-Cl H Z3.37 H SMe Cl 6′-Cl H Z3.38 Me SMe Cl 6′-Cl HZ3.39 H SEt Cl 6′-Cl H Z3.40 Me SEt Cl 6′-Cl H Z3.41 H OMe Cl 6′-Br HZ3.42 Me OMe Cl 6′-Br H Z3.43 H OEt Cl 6′-Br H Z3.44 Me OEt Cl 6′-Br HZ3.45 H SMe Cl 6′-Br H Z3.46 Me SMe Cl 6′-Br H Z3.47 H SEt Cl 6′-Br HZ3.48 Me SEt Cl 6′-Br H Z3.49 H OMe Cl

H Z3.50 Me OMe Cl

H Z3.51 H OEt Cl

H Z3.52 Me OEt Cl

H Z3.53 H SMe Cl

H Z3.54 Me SMe Cl

H Z3.55 H SEt Cl

H Z3.56 Me SEt Cl

H Z3.57 H OMe Cl

H Z3.58 Me OMe Cl

H Z3.59 H OEt Cl

H Z3.60 Me OEt Cl

H Z3.61 H SMe Cl

H Z3.62 Me SMe Cl

H Z3.63 H SEt Cl

H Z3.64 Me SEt Cl

H

TABLE 37 Compounds of formula III-1 The invention is further illustratedby the preferred individual compounds of formula (II-1) listed below inTable 37. Characterising data is given in Table 40. (III-1)

Com- pound Num- ber R₁ XR₃ R_(5a) R_(5b) R_(5c) Z4.1 H OMe Cl Cl H Z4.2Me OMe Cl Cl H Z4.3 H OMe Cl Br H Z4.4 Me OMe Cl Br H Z4.5 H OEt Cl Cl HZ4.6 Me OEt Cl Cl H Z4.7 H OEt Cl Br H Z4.8 Me OEt Cl Br H Z4.9 H SMe ClCl H Z4.10 Me SMe Cl Cl H Z4.11 H SMe Cl Br H Z4.12 Me SMe Cl Br H Z4.13H SEt Cl Cl H Z4.14 Me SEt Cl Cl H Z4.15 H SEt Cl Br H Z4.16 Me SEt ClBr H Z4.17 H OMe Cl

H Z4.18 Me OMe Cl

H Z4.19 H OEt Cl

H Z4.20 Me OEt Cl

H Z4.21 H OMe Cl

H Z4.22 Me OMe Cl

H Z4.23 H OEt Cl

H Z4.24 Me OEt Cl

H Z4.25 H OMe Cl

H Z4.26 Me OMe Cl

H Z4.27 H OEt Cl

H Z4.28 Me OEt Cl

H Z4.29 H OMe Cl

H Z4.30 Me OMe Cl

H Z4.31 H OEt Cl

H Z4.32 Me OEt Cl

H Z4.33 H OMe Cl

H Z4.34 Me OMe Cl

H Z4.35 H OEt Cl

H Z4.36 Me OEt Cl

H Z4.37 H OMe Cl

H Z4.38 Me OMe Cl

H Z4.39 H OEt Cl

H Z4.40 Me OEt Cl

H Z4.41 H OMe Cl H H Z4.42 Me OMe Cl H H Z4.43 H OEt Cl H H Z4.44 Me OEtCl H H Z4.45 H SMe Cl H H Z4.46 Me SMe Cl H H Z4.47 H SEt Cl H H Z4.48Me SEt Cl H H

TABLE 38 Compounds of formula III-2 The invention is further illustratedby the preferred individual compounds of formula (III-2) listed below inTable 38. Characterising data is given in Table 40. (III-2)

Com- pound Num- ber R₁ XR₃ R_(5a) R_(5b) R_(5c) Z5.1 H OMe Cl

Cl Z5.2 Me OMe Cl

Cl Z5.3 H OEt Cl

Cl Z5.4 Me OEt Cl

Cl Z5.5 H SMe Cl

Cl Z5.6 Me SMe Cl

Cl Z5.7 H SEt Cl

Cl Z5.8 Me SEt Cl

Cl Z5.9 H OMe Cl Cl

Z5.10 Me OMe Cl Cl

Z5.11 H OEt Cl Cl

Z5.12 Me OEt Cl Cl

Z5.13 H SMe Cl Cl

Z5.14 Me SMe Cl Cl

Z5.15 H SEt Cl Cl

Z5.16 Me SEt Cl Cl

Z5.17 H OMe Cl

Cl Z5.18 Me OMe Cl

Cl Z5.19 H OEt Cl

Cl Z5.20 Me OEt Cl

Cl Z5.21 H SMe Cl

Cl Z5.22 Me SMe Cl

Cl Z5.23 H SEt Cl

Cl Z5.24 Me SEt Cl

Cl Z5.25 H OMe Cl Cl

Z5.26 Me OMe Cl Cl

Z5.27 H OEt Cl Cl

Z5.28 Me OEt Cl Cl

Z5.29 H SMe Cl Cl

Z5.30 Me SMe Cl Cl

Z5.31 H SEt Cl Cl

Z5.32 Me SEt Cl Cl

Z5.33 H OMe Cl

Cl Z5.34 Me OMe Cl

Cl Z5.35 H OEt Cl

Cl Z5.36 Me OEt Cl

Cl Z5.37 H SMe Cl

Cl Z5.38 Me SMe Cl

Cl Z5.39 H SEt Cl

Cl Z5.40 Me SEt Cl

Cl Z5.41 H OMe Cl Cl

Z5.42 Me OMe Cl Cl

Z5.43 H OEt Cl Cl

Z5.44 Me OEt Cl Cl

Z5.45 H SMe Cl Cl

Z5.46 Me SMe Cl Cl

Z5.47 H SEt Cl Cl

Z5.48 Me SEt Cl Cl

Z5.49 H OMe Cl

Cl Z5.50 Me OMe Cl

Cl Z5.51 H OEt Cl

Cl Z5.52 Me OEt Cl

Cl Z5.53 H SMe Cl

Cl Z5.54 Me SMe Cl

Cl Z5.55 H SEt Cl

Cl Z5.56 Me SEt Cl

Cl Z5.57 H OMe Cl Cl

Z5.58 Me OMe Cl Cl

Z5.59 H OEt Cl Cl

Z5.60 Me OEt Cl Cl

Z5.61 H SMe Cl Cl

Z5.62 Me SMe Cl Cl

Z5.63 H SEt Cl Cl

Z5.64 Me SEt Cl Cl

Z5.65 H OMe Cl

Cl Z5.66 Me OMe Cl

Cl Z5.67 H OEt Cl

Cl Z5.68 Me OEt Cl

Cl Z5.69 H SMe Cl

Cl Z5.70 Me SMe Cl

Cl Z5.71 H SEt Cl

Cl Z5.72 Me SEt Cl

Cl Z5.73 H OMe Cl Cl

Z5.74 Me OMe Cl Cl

Z5.75 H OEt Cl Cl

Z5.76 Me OEt Cl Cl

Z5.77 H SMe Cl Cl

Z5.78 Me SMe Cl Cl

Z5.79 H SEt Cl Cl

Z5.80 Me SEt Cl Cl

Z5.81 H OMe Cl

Cl Z5.82 Me OMe Cl

Cl Z5.83 H OEt Cl

Cl Z5.84 Me OEt Cl

Cl Z5.85 H SMe Cl

Cl Z5.86 Me SMe Cl

Cl Z5.87 H SEt Cl

Cl Z5.88 Me SEt Cl

Cl Z5.89 H OMe Cl Cl

Z5.90 Me OMe Cl Cl

Z5.91 H OEt Cl Cl

Z5.92 Me OEt Cl Cl

Z5.93 H SMe Cl Cl

Z5.94 Me SMe Cl Cl

Z5.95 H SEt Cl Cl

Z5.96 Me SEt Cl Cl

Z5.97 H OMe Cl Cl Cl Z5.98 Me OMe Cl Cl Cl Z5.99 H OEt Cl Cl Cl Z5.100Me OEt Cl Cl Cl Z5.101 H SMe Cl Cl Cl Z5.102 Me SMe Cl Cl Cl Z5.103 HSEt Cl Cl Cl Z5.104 Me SEt Cl Cl Cl Z5.105 H OMe Cl H Cl Z5.106 Me OMeCl H Cl Z5.107 H OEt Cl H Cl Z5.108 Me OEt Cl H Cl Z5.109 H SMe Cl H ClZ5.110 Me SMe Cl H Cl Z5.111 H SEt Cl H Cl Z5.112 Me SEt Cl H Cl Z5.113H OMe Cl Cl H Z5.114 Me OMe Cl Cl H Z5.115 H OEt Cl Cl H Z5.116 Me OEtCl Cl H Z5.117 H SMe Cl Cl H Z5.118 Me SMe Cl Cl H Z5.119 H SEt Cl Cl HZ5.120 Me SEt Cl Cl H Z5.121 H OMe Cl Br Cl Z5.122 Me OMe Cl Br ClZ5.123 H OEt Cl Br Cl Z5.124 Me OEt Cl Br Cl Z5.125 H SMe Cl Br ClZ5.126 Me SMe Cl Br Cl Z5.127 H SEt Cl Br Cl Z5.128 Me SEt Cl Br ClZ5.129 H OMe Cl Cl Br Z5.130 Me OMe Cl Cl Br Z5.131 H OEt Cl Cl BrZ5.132 Me OEt Cl Cl Br Z5.133 H SMe Cl Cl Br Z5.134 Me SMe Cl Cl BrZ5.135 H SEt Cl Cl Br Z5.136 Me SEt Cl Cl Br

TABLE 39 Compounds of formula III-3 The invention is further illustratedby the preferred individual compounds of formula (III-3) listed below inTable 39. Characterising data is given in Table 40. (III-3)

Compound Number R₁ XR₃ R_(5a) R_(5b) R_(5c) Z6.1 H OMe Cl 5′-Cl H Z6.2Me OMe Cl 5′-Cl H Z6.3 H OEt Cl 5′-Cl H Z6.4 Me OEt Cl 5′-Cl H Z6.5 HSMe Cl 5′-Cl H Z6.6 Me SMe Cl 5′-Cl H Z6.7 H SEt Cl 5′-Cl H Z6.8 Me SEtCl 5′-Cl H Z6.9 H OMe Cl 5′-Br H Z6.10 Me OMe Cl 5′-Br H Z6.11 H OEt Cl5′-Br H Z6.12 Me OEt Cl 5′-Br H Z6.13 H SMe Cl 5′-Br H Z6.14 Me SMe Cl5′-Br H Z6.15 H SEt Cl 5′-Br H Z6.16 Me SEt Cl 5′-Br H Z6.17 H OMe Cl

H Z6.18 Me OMe Cl

H Z6.19 H OEt Cl

H Z6.20 Me OEt Cl

H Z6.21 H SMe Cl

H Z6.22 Me SMe Cl

H Z6.23 H SEt Cl

H Z6.24 Me SEt Cl

H Z6.25 H OMe Cl

H Z6.26 Me OMe Cl

H Z6.27 H OEt Cl

H Z6.28 Me OEt Cl

H Z6.29 H SMe Cl

H Z6.30 Me SMe Cl

H Z6.31 H SEt Cl

H Z6.32 Me SEt Cl

H Z6.33 H OMe Cl 6′-Cl H Z6.34 Me OMe Cl 6′-Cl H Z6.35 H OEt Cl 6′-Cl HZ6.36 Me OEt Cl 6′-Cl H Z6.37 H SMe Cl 6′-Cl H Z6.38 Me SMe Cl 6′-Cl HZ6.39 H SEt Cl 6′-Cl H Z6.40 Me SEt Cl 6′-Cl H Z6.41 H OMe Cl 6′-Br HZ6.42 Me OMe Cl 6′-Br H Z6.43 H OEt Cl 6′-Br H Z6.44 Me OEt Cl 6′-Br HZ6.45 H SMe Cl 6′-Br H Z6.46 Me SMe Cl 6′-Br H Z6.47 H SEt Cl 6′-Br HZ6.48 Me SEt Cl 6′-Br H Z6.49 H OMe Cl

H Z6.50 Me OMe Cl

H Z6.51 H OEt Cl

H Z6.52 Me OEt Cl

H Z6.53 H SMe Cl

H Z6.54 Me SMe Cl

H Z6.55 H SEt Cl

H Z6.56 Me SEt Cl

H Z6.57 H OMe Cl

H Z6.58 Me OMe Cl

H Z6.59 H OEt Cl

H Z6.60 Me OEt Cl

H Z6.61 H SMe Cl

H Z6.62 Me SMe Cl

H Z6.63 H SEt Cl

H Z6.64 Me SEt Cl

H

Physical Data (Melting Points in ° C.):

Throughout this description, temperatures are given in degrees Celsius;“NMR” means nuclear magnetic resonance spectrum; MS is mass spectrum;and “%” is percent by weight, unless corresponding concentrations areindicated in other units.

The following abbreviations are used throughout this description:

m.p. = melting point b.p. = boiling point. S = singlet br = broad d =doublet dd = doublet of doublets t = triplet q = quartet m = multipletppm = parts per million

Table 40 shows selected melting points, and NMR data, all with CDCl₃ assolvent, if not otherwise stated; if a mixture of solvents is present,this is indicated as, for example, (CDCl₃/d₆-DMSO).

TABLE 40 ¹H-NMR data: Cpd No. (ppm/multiplicity/number of Hs). m.p./(°C.) 22.2 — 128-132 22.4 — 115-125 22.33 — 139-141 22.34 — 150-155 22.36— 130-135 25.34 — resin 29.34 — resin 30.2 — 115-125 30.4 — 112-11630.33 — 117-120 30.34 — resin 33.1 — resin 33.2 — 125-130 33.4 — 100-10433.33 — 141-143 33.34 — resin 33.36 — 150-155

Tables 1a to 13a: Compounds of Formula I-1a

The invention is further illustrated by the preferred individualcompounds of formula (I-1a) listed below in Tables 1a to 13a.

Each of Tables 1a to 13a, which follow the Table Va below, comprises 48compounds of the formula (I-1a) in which R₁, X—R₃, R_(5a), R_(5b) andR_(5c), have the values given in Table Va and A has the value given inthe relevant Table 1a to 13a. Thus Table 1a corresponds to Table Va whenVa is 1 and A has the value given under the Table 1a heading, Table 2acorresponds to Table V when Va is 2 and A has the value given under theTable 2a heading, and so on for Tables 3a to 13a.

TABLE Va Compound Number R₁ XR₃ R_(5a) R_(5b) R_(5c) Va.1 H OMe Cl Cl HVa.2 Me OMe Cl Cl H Va.3 H OMe Cl Br H Va.4 Me OMe Cl Br H Va.5 H OEt ClCl H Va.6 Me OEt Cl Cl H Va.7 H OEt Cl Br H Va.8 Me OEt Cl Br H Va.9 HSMe Cl Cl H Va.10 Me SMe Cl Cl H Va.11 H SMe Cl Br H Va.12 Me SMe Cl BrH Va.13 H SEt Cl Cl H Va.14 Me SEt Cl Cl H Va.15 H SEt Cl Br H Va.16 MeSEt Cl Br H Va.17 H OMe Cl

H Va.18 Me OMe Cl

H Va.19 H OEt Cl

H Va.20 Me OEt Cl

H Va.21 H OMe Cl

H Va.22 Me OMe Cl

H Va.23 H OEt Cl

H Va.24 Me OEt Cl

H Va.25 H OMe Cl

H Va.26 Me OMe Cl

H Va.27 H OEt Cl

H Va.28 Me OEt Cl

H Va.29 H OMe Cl

H Va.30 Me OMe Cl

H Va.31 H OEt Cl

H Va.32 Me OEt Cl

H Va.33 H OMe Cl

H Va.34 Me OMe Cl

H Va.35 H OEt Cl

H Va.36 Me OEt Cl

H Va.37 H OMe Cl

H Va.38 Me OMe Cl

Va.39 H OEt Cl

H Va.40 Me OEt Cl

H Va.41 H OMe Cl H H Va.42 Me OMe Cl H H Va.43 H OEt Cl H H Va.44 Me OEtCl H H Va.45 H SMe Cl H H Va.46 Me SMe Cl H H Va.47 H SEt Cl H H Va.48Me SEt Cl H H

Table 1a provides 48 compounds of formula (I-1a), wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va. For example, compound 1a.1 has the followingstructure:

Table 2a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 3a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 4a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 5a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 6a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 7a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 8a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 9a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 10a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 11a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 12a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Table 13a provides 48 compounds of formula (I-1a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Va.

Tables 14a to 20a: Compounds of Formula I-2a:

The invention is further illustrated by the preferred individualcompounds of formula (I-2a) listed below in Tables 14a to 20a.

Each of Tables 14a to 20a, which follow the Table Wa below, comprises136 compounds of the formula (I-2a) in which R₁, X—R₃, R_(5a), R_(5b)and R_(5c) have the values given in Table Wa and A has the value givenin the relevant Table 14a to 20a. Thus Table 14 corresponds to Table Wawhen Wa is 14 and A has the value given under the Table 14a heading,Table 15a corresponds to Table Wa when Wa is 15 and A has the valuegiven under the Table 15a heading, and so on for Tables 16a to 20a.

TABLE Wa Compound Number R₁ XR₃ R_(5a) R_(5b) R_(5c) Wa.1 H OMe Cl

Cl Wa.2 Me OMe Cl

Cl Wa.3 H OEt Cl

Cl Wa.4 Me OEt Cl

Cl Wa.5 H SMe Cl

Cl Wa.6 Me SMe Cl

Cl Wa.7 H SEt Cl

Cl Wa.8 Me SEt Cl

Cl Wa.9 H OMe Cl Cl

Wa.10 Me OMe Cl Cl

Wa.11 H OEt Cl Cl

Wa.12 Me OEt Cl Cl

Wa.13 H SMe Cl Cl

Wa.14 Me SMe Cl Cl

Wa.15 H SEt Cl Cl

Wa.16 Me SEt Cl Cl

Wa.17 H OMe Cl

Cl Wa.18 Me OMe Cl

Cl Wa.19 H OEt Cl

Cl Wa.20 Me OEt Cl

Cl Wa.21 H SMe Cl

Cl Wa.22 Me SMe Cl

Cl Wa.23 H SEt Cl

Cl Wa.24 Me SEt Cl

Cl Wa.25 H OMe Cl Cl

Wa.26 Me OMe Cl Cl

Wa.27 H OEt Cl Cl

Wa.28 Me OEt Cl Cl

Wa.29 H SMe Cl Cl

Wa.30 Me SMe Cl Cl

Wa.31 H SEt Cl Cl

Wa.32 Me SEt Cl Cl

Wa.33 H OMe Cl

Cl Wa.34 Me OMe Cl

Cl Wa.35 H OEt Cl

Cl Wa.36 Me OEt Cl

Cl Wa.37 H SMe Cl

Cl Wa.38 Me SMe Cl

Cl Wa.39 H SEt Cl

Cl Wa.40 Me SEt Cl

Cl Wa.41 H OMe Cl Cl

Wa.42 Me OMe Cl Cl

Wa.43 H OEt Cl Cl

Wa.44 Me OEt Cl Cl

Wa.45 H SMe Cl Cl

Wa.46 Me SMe Cl Cl

Wa.47 H SEt Cl Cl

Wa.48 Me SEt Cl Cl

Wa.49 H OMe Cl

Cl Wa.50 Me OMe Cl

Cl Wa.51 H OEt Cl

Cl Wa.52 Me OEt Cl

Cl Wa.53 H SMe Cl

Cl Wa.54 Me SMe Cl

Cl Wa.55 H SEt Cl

Cl Wa.56 Me SEt Cl

Cl Wa.57 H OMe Cl Cl

Wa.58 Me OMe Cl Cl

Wa.59 H OEt Cl Cl

Wa.60 Me OEt Cl Cl

Wa.61 H SMe Cl Cl

Wa.62 Me SMe Cl Cl

Wa.63 H SEt Cl Cl

Wa.64 Me SEt Cl Cl

Wa.65 H OMe Cl

Cl Wa.66 Me OMe Cl

Cl Wa.67 H OEt Cl

Cl Wa.68 Me OEt Cl

Cl Wa.69 H SMe Cl

Cl Wa.70 Me SMe Cl

Cl Wa.71 H SEt Cl

Cl Wa.72 Me SEt Cl

Cl Wa.73 H OMe Cl Cl

Wa.74 Me OMe Cl Cl

Wa.75 H OEt Cl Cl

Wa.76 Me OEt Cl Cl

Wa.77 H SMe Cl Cl

Wa.78 Me SMe Cl Cl

Wa.79 H SEt Cl Cl

Wa.80 Me SEt Cl Cl

Wa.81 H OMe Cl

Cl Wa.82 Me OMe Cl

Cl Wa.83 H OEt Cl

Cl Wa.84 Me OEt Cl

Cl Wa.85 H SMe Cl

Cl Wa.86 Me SMe Cl

Cl Wa.87 H SEt Cl

Cl Wa.88 Me SEt Cl

Cl Wa.89 H OMe Cl Cl

Wa.90 Me OMe Cl Cl

Wa.91 H OEt Cl Cl

Wa.92 Me OEt Cl Cl

Wa.93 H SMe Cl Cl

Wa.94 Me SMe Cl Cl

Wa.95 H SEt Cl Cl

Wa.96 Me SEt Cl Cl

Wa.97 H OMe Cl Cl Cl Wa.98 Me OMe Cl Cl Cl Wa.99 H OEt Cl Cl Cl Wa.100Me OEt Cl Cl Cl Wa.101 H SMe Cl Cl Cl Wa.102 Me SMe Cl Cl Cl Wa.103 HSEt Cl Cl Cl Wa.104 Me SEt Cl Cl Cl Wa.105 H OMe Cl H Cl Wa.106 Me OMeCl H Cl Wa.107 H OEt Cl H Cl Wa.108 Me OEt Cl H Cl Wa.109 H SMe Cl H ClWa.110 Me SMe Cl H Cl Wa.111 H SEt Cl H Cl Wa.112 Me SEt Cl H Cl Wa.113H OMe Cl Cl H Wa.114 Me OMe Cl Cl H Wa.115 H OEt Cl Cl H Wa.116 Me OEtCl Cl H Wa.117 H SMe Cl Cl H Wa.118 Me SMe Cl Cl H Wa.119 H SEt Cl Cl HWa.120 Me SEt Cl Cl H Wa.121 H OMe Cl Br Cl Wa.122 Me OMe Cl Br ClWa.123 H OEt Cl Br Cl Wa.124 Me OEt Cl Br Cl Wa.125 H SMe Cl Br ClWa.126 Me SMe Cl Br Cl Wa.127 H SEt Cl Br Cl Wa.128 Me SEt Cl Br ClWa.129 H OMe Cl Cl Br Wa.130 Me OMe Cl Cl Br Wa.131 H OEt Cl Cl BrWa.132 Me OEt Cl Cl Br Wa.133 H SMe Cl Cl Br Wa.134 Me SMe Cl Cl BrWa.135 H SEt Cl Cl Br Wa.136 Me SEt Cl Cl Br

Table 14a provides 136 compounds of formula (I-2a), wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Wa.

Table 15a provides 136 compounds of formula (I-2a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Wa.

Table 16a provides 136 compounds of formula (I-2a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Wa.

Table 17a provides 136 compounds of formula (I-2a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Wa.

Table 18a provides 136 compounds of formula (I-2a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Wa.

Table 19a provides 136 compounds of formula (I-2a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c), are asdefined in Table Wa.

Table 20a provides 136 compounds of formula (I-2a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Wa.

Tables 21a to 33a: Compounds of Formula I-3a:

The invention is further illustrated by the preferred individualcompounds of formula (I-3a) listed below in Tables 21a to 33a.

Each of Tables 21a to 33a, which follow the Table Ya below, comprises 64compounds of the formula (I-3a) in which R₁, X—R₃, R_(5a), R_(5b) andR_(5c) have the values given in Table Ya and A has the value given inthe relevant Table 21a to 33a. Thus Table 21a corresponds to Table Yawhen Ya is 21 and A has the value given under the Table 21a heading,Table 22a corresponds to Table Ya when Ya is 22 and A has the valuegiven under the Table 22a heading, and so on for Tables 23a to 33a.

TABLE Ya Compound Number R₁ XR₃ R_(5a) R_(5b) R_(5c) Ya.1 H OMe Cl 5′-ClH Ya.2 Me OMe Cl 5′-Cl H Ya.3 H OEt Cl 5′-Cl H Ya.4 Me OEt Cl 5′-Cl HYa.5 H SMe Cl 5′-Cl H Ya.6 Me SMe Cl 5′-Cl H Ya.7 H SEt Cl 5′-Cl H Ya.8Me SEt Cl 5′-Cl H Ya.9 H OMe Cl 5′-Br H Ya.10 Me OMe Cl 5′-Br H Ya.11 HOEt Cl 5′-Br H Ya.12 Me OEt Cl 5′-Br H Ya.13 H SMe Cl 5′-Br H Ya.14 MeSMe Cl 5′-Br H Ya.15 H SEt Cl 5′-Br H Ya.16 Me SEt Cl 5′-Br H Ya.17 HOMe Cl

H Ya.18 Me OMe Cl

H Ya.19 H OEt Cl

H Ya.20 Me OEt Cl

H Ya.21 H SMe Cl

H Ya.22 Me SMe Cl

H Ya.23 H SEt Cl

H Ya.24 Me SEt Cl

H Ya.25 H OMe Cl

H Ya.26 Me OMe Cl

H Ya.27 H OEt Cl

H Ya.28 Me OEt Cl

H Ya.29 H SMe Cl

H Ya.30 Me SMe Cl

H Ya.31 H SEt Cl

H Ya.32 Me SEt Cl

H Ya.33 H OMe Cl 6′-Cl H Ya.34 Me OMe Cl 6′-Cl H Ya.35 H OEt Cl 6′-Cl HYa.36 Me OEt Cl 6′-Cl H Ya.37 H SMe Cl 6′-Cl H Ya.38 Me SMe Cl 6′-Cl HYa.39 H SEt Cl 6′-Cl H Ya.40 Me SEt Cl 6′-Cl H Ya.41 H OMe Cl 6′-Br HYa.42 Me OMe Cl 6′-Br H Ya.43 H OEt Cl 6′-Br H Ya.44 Me OEt Cl 6′-Br HYa.45 H SMe Cl 6′-Br H Ya.46 Me SMe Cl 6′-Br H Ya.47 H SEt Cl 6′-Br HYa.48 Me SEt Cl 6′-Br H Ya.49 H OMe Cl

H Ya.50 Me OMe Cl

H Ya.51 H OEt Cl

H Ya.52 Me OEt Cl

H Ya.53 H SMe Cl

H Ya.54 Me SMe Cl

H Ya.55 H SEt Cl

H Ya.56 Me SEt Cl

H Ya.57 H OMe Cl

H Ya.58 Me OMe Cl

H Ya.59 H OEt Cl

H Ya.60 Me OEt Cl

H Ya.61 H SMe Cl

H Ya.62 Me SMe Cl

H Ya.63 H SEt Cl

H Ya.64 Me SEt Cl

H

Table 21a provides 64 compounds of formula (I-3a), wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 22a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 23a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 24a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 25a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 26a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 27a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 28a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 29a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 30a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 31a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table.

Table 32a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

Table 33a provides 64 compounds of formula (I-3a) wherein A is

wherein the dashed lines indicate the point of attachment of the group Ato the amide group, and R₁, X—R₃, R_(5a), R_(5b) and R_(5c) are asdefined in Table Ya.

FORMULATION EXAMPLES FOR COMPOUNDS OF FORMULA I Example F-1.1 to F-1.2Emulsifiable Concentrates

Components F-1.1 F-1.2 compound of Tables 1 to 33 25% 50% calciumdodecylbenzenesulfonate  5%  6% castor oil polyethylene glycol ether  5%— (36 mol ethylenoxy units) tributylphenolpolyethylene glycol ether — 4% (30 mol ethylenoxy units) cyclohexanone — 20% xylene mixture 65% 20%

Emulsions of any desired concentration can be prepared by diluting suchconcentrates with water.

Example F-2 Emulsifiable concentrate

Components F-2 compound of Tables 1 to 33 10% octylphenolpolyethyleneglycol ether 3% (4 to 5 mol ethylenoxy units) calciumdodecylbenzenesulfonate 3% castor oil polyglycol ether 4% (36 molethylenoxy units) cyclohexanone 30% xylene mixture 50%

Emulsions of any desired concentration can be prepared by diluting suchconcentrates with water.

Examples F-3.1 to F-3.4 Solutions

Components F-3.1 F-3.2 F-3.3 F-3.4 compound of Tables 1 to 33 80% 10% 5%95% propylene glycol monomethyl ether 20% — — — polyethylene glycol(relative molecular — 70% — — mass: 400 atomic mass units)N-methylpyrrolid-2-one — 20% — — epoxidised coconut oil — — 1%  5%benzin (boiling range: 160-190°) — — 94%  —

The solutions are suitable for use in the form of microdrops.

Examples F-4.1 to F-4.4 Granulates

Components F-4.1 F-4.2 F-4.3 F-4.4 compound of Tables 1 to 33 5% 10%  8%21% kaolin 94%  — 79% 54% highly dispersed silicic acid 1% — 13%  7%attapulgite — 90% — 18%

The novel compound is dissolved in dichloromethane, the solution issprayed onto the carrier and the solvent is then removed by distillationunder vacuum.

Examples F-5.1 and F-5.2 Dusts

Components F-5.1 F-5.2 compound of Tables 1 to 33 2% 5% highly dispersedsilicic acid 1% 5% talcum 97%  — kaolin — 90% 

Ready for use dusts are obtained by intimately mixing all components.

Examples F-6.1 to F-6.3 Wettable Powders

Components F-6.1 F-6.2 F-6.3 compound of Tables 1 to 33 25%  50% 75%sodium lignin sulfonate 5%  5% — sodium lauryl sulfate 3% —  5% sodiumdiisobutylnaphthalene sulfonate —  6% 10% octylphenolpolyethylene glycolether —  2% — (7 to 8 mol ethylenoxy units) highly dispersed silicicacid 5% 10% 10% kaolin 62%  27% —

All components are mixed and the mixture is thoroughly ground in asuitable mill to give wettable powders which can be diluted with waterto suspensions of any desired concentration.

Example F7 Flowable Concentrate for Seed Treatment

compound of Tables 1 to 33 40%  propylene glycol 5% copolymer butanolPO/EO 2% tristyrenephenole with 10-20 moles EO 2%1,2-benzisothiazolin-3-one (in the form of a 20% solution in 0.5%  water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a75% emulsion in water) 0.2%   Water 45.3%  

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

BIOLOGICAL EXAMPLES: FUNGICIDAL ACTIONS Example B-1 Action AgainstBotrytis cinerea/Tomato (Botrytis on Tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application tomato plants are inoculated by spraying a sporesuspension (1×10⁵ conidia/ml) on the test plants. After an incubationperiod of 4 days at 20° C. and 95% r.h. in a growth chamber the diseaseincidence is assessed. Compounds 22.2, 22.4, 22.33, 22.34, 22.36, 30.2,30.4 and 33.2 show good activity in this test (<20% infestation).

Example B-2 Action Against Uncinula Necator/Grape (Powdery Mildew onGrape)

5 week old grape seedlings cv. Gutedel are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. One dayafter application, the grape plants are inoculated by shaking plantsinfected with grape powdery mildew above the test plants. After anincubation period of 7 days at 26° C. and 60% r.h. under a light regimeof 14/10 hours (light/dark) the disease incidence is assessed. Compounds22.2, 22.4, 22.33, 22.34, 22.36, 25.34, 29.34, 30.4, 30.33, 30.34, 33.2,33.4, 33.33, 33.34 and 33.36 show good activity in this test (<20%infestation).

Example B-3 Action Against Puccinia recondita/Wheat (Brownrust on Wheat)

1 week old wheat plants cv. Arina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, the wheat plants are inoculated by spraying a sporesuspension (1×10⁵ uredospores/ml) on the test plants. After anincubation period of 2 days at 20° C. and 95% r.h. the plants are keptin a greenhouse for 8 days at 20° C. and 60% r.h. The disease incidenceis assessed 10 days after inoculation. Compounds 22.2, 22.4 and 22.36show good activity in this test (<20% infestation).

Example B-4 Action Against Septoria tritici/Wheat (Septoria Leaf Spot onWheat)

2 week old wheat plants cv. Riband are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, wheat plants are inoculated by spraying a spore suspension(10×10⁵ conidia/ml) on the test plants. After an incubation period of 1day at 23° C. and 95% r.h., the plants are kept for 16 days at 23° C.and 60% r.h. in a greenhouse. The disease incidence is assessed 18 daysafter inoculation.

Compounds 22.2, 22.4, 22.33, 22.34, 22.36, 25.34, 29.34, 30.2, 30.4,30.33, 30.34, 33.2, 33.4, 33.33, 33.34 and 33.36 show good activity inthis test (<20% infestation).

Example B-5 Action Against Pvrenophora teres/Barley (Net Blotch onBarley)

1 week old barley plants cv. Express are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application barley plants are inoculated by spraying a sporesuspension (3×10⁴ conidia/ml) on the test plants. After an incubationperiod of 2 days at 20° C. and 95% r.h. plants are kept for 2 days at20° C. and 60% r.h. in a greenhouse. The disease incidence is assessed 4days after inoculation. Compounds Compounds 22.2, 22.4, 22.33, 22.34,22.36, 25.34, 29.34, 30.2, 30.4, 30.33, 30.34, 33.2, 33.4, 33.33, 33.34and 33.36 show good activity in this test (<20% infestation).

Example B-6 Action Against Alternaria solani/Tomato (Early Blight onTomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application, the tomato plants are inoculated by spraying a sporesuspension (2×10⁵ conidia/ml) on the test plants. After an incubationperiod of 3 days at 20° C. and 95% r.h. in a growth chamber the diseaseincidence is assessed. Compounds 22.2, 22.4, 22.34, 22.36, 25.34, 29.34,30.2, 30.4, 30.34, 33.2, 33.4, 33.33, 33.34 and 33.36 show good activityin this test (<20% infestation).

1. A compound of the formula I

wherein R₁, R₂ and R₄ independently of each other are hydrogen, halogen,C₁-C₄ alkyl or C₁-C₄ halogenalkyl; X is oxygen, sulfur, —N(R₉)— or—N(R₁₀)—O—; R₉ and R₁₀ independently of each other are hydrogen orC₁-C₆alkyl; R₃ is C₁-C₆alkyl or C₁-C₆haloalkyl; Q is Q₁

or Q is Q₂

wherein each R₅ independently of each other is halogen, C₁-C₄ alkyl,C₁-C₄ halogenalkyl, phenyl, halogenphenyl, C₃-C₇ cycloalkyl acetynyl,phenyl acetynyl or halogenphenyl acetynyl; n is 1, 2 or 3; m is 1, 2, 3or 4; A is a 5- or 6-membered heterocyclic ring containing one to threeheteroatoms, each independently selected from oxygen, nitrogen andsulphur, or a phenyl ring; the heterocyclic ring or the phenyl beingsubstituted by the groups R₆, R₇ and R₈; R₆, R₇ and R₈ are each,independently, hydrogen, halogen, cyano, nitro, C₁₋₄ alkyl, C₁₋₄halogenalkyl, C₁₋₄ halogenalkoxy, C₁₋₄ alkoxy(C₁₋₄)alkyl or C₁₋₄halogenalkoxy(C₁₋₄)alkyl, provided that at least one of R₆, R₇ and R₈ isnot hydrogen; R₁₅ is hydrogen or C₃-C₇cycloalkyl; andtautomers/isomers/enantiomers of these compounds.
 2. A compound offormula I according to claim 1, wherein R₁₅ is hydrogen.
 3. A compoundof formula I according to claim 1, wherein A is a 5-memberedheterocyclic ring containing one to three heteroatoms, eachindependently selected from oxygen, nitrogen and sulphur; theheterocyclic ring being substituted by the groups R₆, R₇ and R₈.
 4. Acompound of formula I according to claim 1, wherein A is A₁

in which R₁₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; R₁₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; and R₁₈ is hydrogen, halogen or cyano; orA is A₂

in which R₂₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; and R₂₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkm-C₁-C₄alkyl; or A is A₃

in which R₃₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; R₃₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; and R₃₈ is hydrogen, halogen or cyano; orA is A₄

in which R₄₆ and R₄₇ independently of one another are halogen, cyano,nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl.
 5. A compoundof formula I according to claim 4, wherein A is A₁.
 6. A compound offormula I according to claim 5, wherein R₁₆ is C₁-C₄alkyl orC₁-C₄halogenalkyl; R₁₇ is C₁-C₄alkyl; and R₁₆ is hydrogen or halogen. 7.A compound of formula I according to claim 1, wherein R₁, R₂ and R₄independently of each other is hydrogen or methyl.
 8. A compound offormula I according to claim 1, wherein Q is Q₂.
 9. A compound offormula I according to claim 11, wherein Q₂ is Q_(2A)

wherein each R₅ independently of each other is halogen, C₁-C₄ alkyl,C₁-C₄ halogenalkyl, phenyl, halogenphenyl, C₃-C₇ cycloalkyl acetynyl,phenyl acetynyl or halogenphenyl acetynyl; and m is 1, 2, 3 or
 4. 10. Acompound of formula I according to claim 9, wherein Q_(2A) is Q_(2A-1),

wherein R_(5a) and R_(5b) are each independently from each otherhalogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl, halogenphenyl, C₃-C₇cycloalkyl acetynyl, phenyl acetynyl or halogenphenyl acetynyl; andR_(5c) is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl.
 11. A compound of formula I according to claim10, wherein R_(5a) is halogen; R_(5b) is halogen, phenyl, halogenphenyl,C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl or halogenphenyl acetynyl;and R_(5c) is hydrogen.
 12. A compound of formula II

wherein Q, X, R₁, R₂, R₃ and R₄ are each as defined in claim
 1. 13. Acompound of formula III

wherein Q, X, R₁, R₂, R₃ and R₄ are each as defined in claim
 1. 14. Amethod of controlling or preventing infestation of useful plants byphytopathogenic microorganisms, wherein a compound of formula Iaccording to claim 1 or a composition, comprising this compound asactive ingredient, is applied to the plants, to parts thereof or thelocus thereof.
 15. A composition for controlling and protecting againstphytopathogenic microorganisms, comprising a compound of formula Iaccording to claim 1 and an inert carrier.